Crystalline Flakes Research Articles

Single Crystalline GeSe Van Der Waals Ribbons With Uniform Layer Stacking, High Carrier Mobility, and Adjustable Edge Morphology.

Performance of the group IV monochalcogenide GeSe in solar cells, electronic, and optoelectronic devices is expected to improve when high-quality single crystalline material is used rather than polycrystalline films. Crystalline flakes represent an attractive alternative to bulk single crystals as their synthesis may be developed to be scalable, faster, and with higher overall yield. However, large - and especially large and thin - single crystal flakes are notoriously hard to synthesize. Here it is demonstrated that vapor-liquid-solid growth combined with direct lateral vapor-solid incorporation produces high-quality single crystalline GeSe ribbons with tens of micrometers size and controllable thickness. Electron microscopy shows that the ribbons exhibit perfect equilibrium (AB) van der Waals stacking order without extended defects across the entire thickness, in contrast to the conventional case of substrate-supported flakes where material is added via layer-by-layer nucleation and growth on the basal plane. Electrical measurements show anisotropic transport and a high Hall mobility of 85 cm2V-1s-1, on par with the best single crystals to date. Growth from mixed GeSe and SnSe vapors, finally, yields ribbons with unchanged structure and composition but with jagged edges, promising for applications that rely on ample chemically active edge sites, such as catalysis or photocatalysis.

Enhancement of antimicrobial properties and cytocompatibility through silver and magnesium doping strategies on copper oxide nanocomposites

In the present study, silver (Ag), magnesium (Mg), and the various molar ratios of Ag:Mg-doped copper oxide nanocomposites (CuO NCs) were synthesized by the co-precipitation method. The CuO NC samples calcined at 500 °C were further analyzed for their morphological, structural, functional, and optical properties. Adding single and dual doping increased the pristine CuO band gap from 1.28 to 1.50 eV. The Ag and Mg metal peaks were revealed in the Fourier transform infrared (FTIR) analysis, while an elevated Mg band was observed in all Mg-doped samples in the Raman results. All CuO NCs showed a monoclinic crystalline structure, flake, and rod-like morphologies. Microbes of Bacillus subtilis, Shigella dysenteriae, and Candida albicans were tested against different concentrations of CuO NCs. Better results for all tested microbes were observed with the 2 mg concentration. The high cytotoxicity effect was observed in the pristine and Cu:Ag (94:6) sample, and other CuO NCs, which demonstrated over 80 % viability in RAW 246.7 cells at a concentration of 0.5 µg/ml. Remarkably, over 94 % cell viability at 0.5 µg/ml was achieved with the Cu:Ag:Mg (94:3:3) NCs ratio, owing to the synergistic effect of the ion-releasing ability of Cu2+, Ag2+, and Mg2+ ions. It possesses a distinctive high aspect ratio shape, is ion-releasing, and has excellent cytocompatibility. The suitability of the Cu:Ag:Mg (94:3:3) NCs ratio for addressing microbial challenges in healthcare is suggested by their distinct characteristics, indicating the promising potential for future biomedical applications.

Sustainable and facile fabrication of chitosan-coated silver-doped zinc oxide nanocomposites exploiting Bergera koenigii foliage for enhanced photocatalysis and antibacterial activity

Industrial and academic chemical pollutants such as Eriochrome Black-T (EBT) and murexide dyes are widely used in academic institution as well as industries, when eluted into rivers, delineate the ill effect on human and aquatic life. Herein, green and ecofriendly synthesis of silver doped-Zinc oxide nanoparticles (Ag/ZnO NPs) and chitosan coated Ag/ZnO nanoparticles (CS/Ag/ZnO NPs) using Bergera koenigii extract to solve environmental issues have been reported for the first time. Spherical and agglomerated particles with crystalline flakes like morphology of Ag/ZnO NPs and CS/Ag/ZnO NPs respectively have been ascertained by Scanning electron morphology (SEM) analyses and XRD. XRD analysis revealed the average crystallite size of 42.16 nm and 48.45 nm for Ag/ZnO NPs with 5 % and 10 % Ag concentration respectively, lesser than crystallite size of 47.394 nm and 52.38 nm for CS-5 % Ag/ZnO NC and CS-10 % Ag/ZnO NC respectively. All the synthesized NPs and NC demonstrated remarkable antibacterial potential against both gram +ve and gram -ve bacteria. Additionally, all the materials showed very high time-dependent photocatalytic degradation activity (>98 %) of EBT and murexide in 12 min. Remarkably, all active nano-catalysts exhibit high durability, and displayed recyclability for >8 cycles. In nutshell, chitosan coated nano-catalyst showed drastic improvement in photocatalytic and antibacterial activities.

(Invited) Manipulating the Exotic Excitons of Van Der Waals Correlated Antiferromagnet with Impurities and Size

A Van der Waals correlated antiferromagnet, metal phosphorus trichalcogenides (MPX3, M = Mn, Fe, Ni; X = S, Se), have emerged as promising candidates for next generation spintronics, and quantum information technologies. Nickel phosphorus trisulfide (NiPS3) is a most notable member of this family and has been extensively studied for its unique properties, including the emergence of an ultra-sharp photoluminescence (PL) peak at ~1.476 eV below Néel temperature of 150 Kelvin. While the highly anisotropic, linearly polarized emission of this PL peak has been shown to be directly correlated to the long-range spin order of NiPS3, its ultra-narrow linewidth of a few hundred meV has led to the speculation that it is originated from a coherent many-body exciton state. Observations of multiple phonon bounds states and formation of exciton-polaritons also creates more excitement as they present new possibilities for design and control of correlated electron systems.Aiming to achieve understanding and control of this spin-correlated exciton, we conduct temperature dependent, polarization resolved, PL studies on compounds of NiPS3 doped with different concentration of Mn (Ni1-xMnxPS3) and Se (NiPS3(1-x)Se3x). We observed systematic variation in characteristics of the spin-correlated exciton revealing their sensitive dependence on disturbance in the magnetic order of NiPS3.Next, to explore the effect of nanostructuring, we developed a novel chemical synthesis for highly crystalline NiPS3 nano flakes. We observed an activation of a new exciton state that share many exciting properties of bulk spin-correlated exciton.

Synthesis of Highly Crystalline Flakes of 3R‐MoS2 and 3R‐WS2 and Their Electrocatalytic and Photocatalytic Hydrogen Evolution Reactivity

AbstractIn the present study, we are able to synthesize flakes of the 3R‐polytypes of MoS2 and WS2 from sodium molybdate and sodium tungstate in the presence of H2S gas by solid‐state reaction. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and X‐ray diffraction are utilized to characterize the morphology, structure, and chemical composition of the 3R‐MoS2 and 3R‐WS2 flakes. The electrocatalytic and photocatalytic activities of 3R‐MoS2 and 3R‐WS2 flakes have been measured in hydrogen evolution reactions.

A feasibility study of oil palm empty fruit bunch pulp as a substitution for radiata pine pulp for autoclave fibre cement composite production

The main objective of this study was to investigate the feasibility of using unbleached pulp from oil palm empty fruit bunches, produced via the Ethanolamine pulping process, to replace Radiata Pine pulp in autoclave fibre cement composite (AFCC) manufacturing. The Ethanolamine pulping process was chosen for its silica retention capability on empty fruit bunch surfaces. The research involves three key phases: an initial characterization of RPP and EFBP properties, including kappa numbers and pulp aspect ratios; subsequent AFCC production with varying RPP content levels (0%–13%) and different cement-to-silica (C/S) ratios (0.2–1.0); and the introduction of EFBP as a partial or complete substitute for RPP at a fixed C/S ratio. Results reveal RPP excels in fibre quality attributes like length, coarseness, fineness, width, and wet/dry zero span, while EFBP offers advantages in fibre count and macro fibrillation index. X-ray diffraction confirms silica presence on EFBP. The highest modulus of rupture (MOR), at 15.5 MPa, is achieved with 9% RPP and a C/S ratio of 1.0. Subsequent analysis, with 1% EFBP interval substitutions to total 13% pulp content, yields the highest MOR values under dry (16.7 MPa) and wet (9.9 MPa) conditions using recipes with 6% RPP and 3% EFBP. XRD confirms the presence of silica on EFBP, forming a crystalline flake layer post-autoclaving. Thus, EFBP proves suitable as a partial AFCC substitute.

Exfoliation of Molecular Solids by the Synergy of Ultrasound and Use of Surfactants: A Novel Method Applied to Boric Acid.

Boric acid, H3BO3, is a molecular solid made up of layers held together by weak van der Waals forces. It can be considered a pseudo "2D" material, like graphite, compared to graphene. The key distinction is that within each individual layer, the molecular units are connected not only by strong covalent bonds but also by hydrogen bonds. Therefore, classic liquid exfoliation is not suitable for this material, and a specific method needs to be developed. Preliminary results of exfoliation of boric acid particles by combination of ultrasound and the use of surfactants are presented. Ultrasound provides the system with the energy needed for the process, and the surfactant can act to keep the crystalline flakes apart. A system consisting of a saturated solution and large excess solid residue of boric acid was treated in this way for a few hours at 40 °C in the presence of various sodium stearate, proving to be very promising, and an incipient exfoliation was achieved.

Gold Recovery from E-Waste by Food-Waste Amyloid Aerogels.

Demand for gold recovery from e-waste grows steadily due to its pervasive use in the most diverse technical applications. Current methods of gold recovery are resource-intensive, necessitating the development of more efficient extraction materials. This study explores protein amyloid nanofibrils (AF) derived from whey, a dairy industry side-stream, as a novel adsorbent for gold recovery from e-waste. To do so, AF aerogels are prepared and assessed against gold adsorption capacity and selectivity over other metals present in waste electrical and electronic equipment (e-waste). The results demonstrate that AF aerogel has a remarkable gold adsorption capacity (166.7mg g-1) and selectivity, making it efficient and an adsorbent for gold recovery. Moreover, AF aerogels are efficient templates to convert gold ions into single crystalline flakes due to Au growth along the (111) plane. When used as templates to recover gold from e-waste solutions obtained by dissolving computer motherboards in suitable solvents, the process yields high-purity gold nuggets, constituted by ≈90.8wt% gold (21-22 carats), with trace amounts of other metals. Life cycle assessment and techno-economic analysis of the process finally consolidate the potential of protein nanofibril aerogels from food side-streams as an environmentally friendly and economically viable approach for gold recovery from e-waste.

Molecularly Confined Topochemical Transformation of MXene Enables Ultrathin Amorphous Metal-Oxide Nanosheets.

Two-dimensional (2D) amorphous nanosheets with ultrathin thicknesses have properties that differ from their crystalline counterparts. However, conventional methods for growing 2D materials often produce either crystalline flakes or amorphous nanosheets with an uncontrollable thickness. Here, we report that ultrathin amorphous metal-oxide nanosheets featuring superior flatness can be realized through the molecularly confined topochemical transformation of MXene. Using MXene Ti2CTx as an example, we show that surface modification of Ti2CTx nanosheets with molecular ligands, such as oleylamine (OAm) and oleic acid (OA), not only imparts notable colloidal dispersity to Ti2CTx nanosheets in nonpolar organic solvents but also confines their subsequent oxidation to in-plane configurations. We demonstrate that unlike the drastic oxidation conventionally observed for pristine MXene, hydrophobizing MXene with OAm and OA ligands enables individual Ti2CTx nanosheets to undergo independent oxidation in a nondestructive manner, resulting in amorphous titanium oxide (am-TiO2) nanosheets that faithfully retain the dimension and flatness of pristine MXene. These am-TiO2 nanosheets exhibit exceptional activity as substrates for surface-enhanced Raman scattering. Importantly, this molecular confinement strategy can be extended to other MXene materials, providing a versatile approach for synthesizing ultrathin amorphous metal-oxide nanosheets with tailored compositions and functionalities.

Natural radioactivity level in graphite samples from the Cătălinul deposit, Parâng Mountains, Romania: sources identification and radiological risk assessment

Twenty graphite samples (amorphous and crystalline flake types of graphite) were collected from the ore storage of the Catalinul deposit and, the 238U, 232Th, 40K naturally occurring radionuclides have been investigated by gamma-ray spectrometry. The mineral contents of selected graphite samples were examined using a scanning electron microscope (SEM). The radiological hazard parameters: radium equivalent activity (Raeq), absorbed gamma dose rates in air (DR), and external hazard index (Hex) were calculated and compared with international safety limits. Radiometric data showed average specific activities for 238U, 232Th and, 40K of 80.40, 49.69 and, 124.21 Bq kg–1 for amorphous graphite respectively, 38.53, 76.25 and, 241.12 Bq kg–1 for flake graphite. Zircon, rutile, uraninite, coffinite, urano-thorite, and monazite are the main radioactive element bearing minerals. The mean of the radiological hazard parameters: Raeq – 262.22 (Bq kg–1), DR – 123.72 (nGy/h), and 0.7 – Hex do not exceed the recommended values by UNSCEAR.

Growth and Local Structures of Single Crystalline Flakes of Three-Dimensional Covalent Organic Frameworks in Water.

Due to the enormous chemical and structural diversities and designable properties and functionalities, covalent organic frameworks (COFs) hold great promise as tailored materials for industrial applications in electronics, biology, and energy technologies. They were typically obtained as partially crystalline materials, although a few single-crystal three-dimensional (3D) COFs have been obtained recently with structures probed by diffraction techniques. However, it remains challenging to grow single-crystal COFs with controlled morphology and to elucidate the local structures of 3D COFs, imposing severe limitations on the applications and understanding of the local structure-property correlations. Herein, we develop a method for designed growth of five types of single crystalline flakes of 3D COFs with controlled morphology, front crystal facets, and defined edge structures as well as surface chemistry using surfactants that can be self-assembled into layered structures to confine crystal growth in water. The flakes enable direct observation of local structures including monomer units, pore structure, edge structure, grain boundary, and lattice distortion of 3D COFs as well as gradually curved surfaces in kinked but single crystalline 3D COFs with a resolution of up to ∼1.7 Å. In comparison with flakes of two-dimensional crystals, the synthesized flakes show much higher chemical, mechanical, and thermal stability.

Hexagonal crystalline nanofillers reinforced composite carbon nanofibers with optimized crystal structure and improved mechanical properties

The mechanical properties of carbon nanofibers (CNFs) are always restricted by their disorganized crystal structures. Herein, this paper utilizes two typical hexagonal crystalline flake materials, nanoscale flake graphite (NG) and hexagonal nitride boron (BN), as nanofillers to optimize the crystal domains of CNFs and achieves enhancement in fiber strength, modulus and toughness. For this purpose, in situ polymerization technique is developed for the rapid and uniform mixing of nanofillers with polyacrylonitrile (PAN) precursors of CNFs. The nanofillers are exfoliated in this process and wrapped with PAN to prevent potential agglomeration. The obtained core-shell nanocomposites can be produced into composite CNFs via electrospinning, stabilization and carbonization. Based on the attraction effect, the dispersed nanofillers can organize PAN molecular chains into oriented crystalline fibrils in as-spun nanofibers and accelerate their transformation to more ladder structures in stabilized nanofibers. On this basis, NG is shown to act as the templating and nucleating agent to promote the formation, growth and compact stacking of graphitic planes in CNFs. BN also improves fiber crystallinity, while its limited templating effect leads to looser and finer crystal domains. As a result, NG-doped CNFs have significantly improved strength and modulus, and BN-doped CNFs possess simultaneously enhanced strength and toughness.

Chemical Vapor Deposition of Er-Doped WS2 Flakes with Near-Infrared Emission and Enhanced Near-Infrared Photoresponse

The electronic and optical properties of two-dimensional transition metal dichalcogenides can be tuned by a doping strategy. Herein, spiral and monolayer Er-doped WS2 (WE) flakes have been synthesized by chemical vapor deposition using ErCl3, WO3, and S as precursors. The growth and properties of WE flakes have been systematically studied based on experimental and theoretical analysis. The morphology, size, and thickness of WE flakes can be regulated by adjusting the molar ratio of ErCl3/WO3 and the growth time. It has been found that the ErCl3 precursor not only acts as the promoter of the WE flakes during the growth but also drives the formation of screw dislocations owing to the internal strain in the lattice induced by Er3+ doping. The WE flakes exhibit near-infrared (NIR) emission at ∼1530 nm under 980 nm excitation, which corresponds to the energy transition from 4I13/2 to 4I15/2 of the Er3+ dopants. In addition, the WE-based device exhibits improved NIR photoresponse with a 16.9-fold enhancement in photocurrent compared with that of the WS2-based device. Our work provides a simple method for the preparation of highly crystalline WE flakes with NIR emission and enhanced NIR photoresponse.

Nonlinear Photoluminescence in Gold Thin Films

Promising applications in photonics are driven by the ability to fabricate crystal-quality metal thin films of controlled thickness down to a few nanometers. In particular, these materials exhibit a highly nonlinear response to optical fields owing to the induced ultrafast electron dynamics, which is however poorly understood on such mesoscopic length scales. Here, we reveal a new mechanism that controls the nonlinear optical response of thin metallic films, dominated by ultrafast electronic heat transport when the thickness is sufficiently small. By experimentally and theoretically studying electronic transport in such materials, we explain the observed temporal evolution of photoluminescence in two-pulse correlation measurements that we report for crystalline gold flakes. Incorporating a first-principles description of the electronic band structure, we model electronic transport and find that ultrafast thermal dynamics plays a pivotal role in determining the strength and time-dependent characteristics of the nonlinear photoluminescence signal, which is largely influenced by the distribution of hot electrons and holes, subject to diffusion across the film as well as relaxation to lattice modes. Our findings introduce conceptually novel elements ruling the nonlinear optical response of nanoscale materials, while suggesting additional ways to control and leverage hot carrier distributions in metallic films.

Influence of graphite geography on the yield of mechanically exfoliated few-layer graphene

Some of graphene's exciting properties that inspired countless studies over the last two decades are exclusive to defect-free, few-layer graphene (FLG, ≤4 layers) produced by mechanical exfoliation. Despite graphite exfoliation having been thoroughly studied, the influence of the graphite source on the successful exfoliation of FLG remains unexplored. In this work, we examine the physicochemical properties and exfoliation performance of various graphite types (e.g., natural crystalline flake, natural vein, and synthetic) from around the globe (e.g., Alaska, Tanzania, China, etc.). We first established a normalization method for the facile comparison of FLG (Φ) yields between separately exfoliated graphites. Using this approach, we find that the relative yield of FLG ranges from 0% to 22% across graphite types, with regular natural crystalline flakes (NCF-R) performing the best overall (ΦNCF-R = 16% ± 5%). FLG yield was also found to depend on source geography, evidenced by ΦNCF-R ranging from 8% to 22% for NCF-R sourced from Alabama and Canada, respectively. We employed machine learning and Pearson correlation analysis to determine the graphite characteristics that govern FLG yield. Graphite source-dependent properties such as graphite surface area and mineral impurities, including aluminum and calcium, were found to be critically important. Our findings highlight the importance of the graphite source when trying to maximize the yield of mechanically exfoliated FLG and represent an important step toward producing higher quantities of defect-free FLG for graphene-based research.

Coaxial heterostructure formation of highly crystalline graphene flakes on boron nitride nanotubes by high-temperature chemical vapor deposition

We develop a high-temperature chemical vapor deposition of highly crystalline graphene on the surface of boron nitride nanotubes (BNNTs). The growth of few-layer graphene flakes on BNNT templates was confirmed by scanning transmission electron microscopy. Based on an investigation of the effect of growth temperature and growth time on defect density, graphene with relatively high crystallinity was obtained at 1350 °C. The absence of undesirable alterations in the BNNT lattice during graphene growth was verified by multiple analyses. The high-temperature growth of heterolayers would assist in the advancement of nanodevices that coaxially combine graphene and boron nitride.

Polymer-Assisted Compressed Flux Growth: A Universal and High-Yield Method for Dimension-Controlled Single Crystals.

Single crystals possess the most perfect and stable morphology and represent the intrinsic and upper limits of performance when integrated into various application scenarios. However, for a large portion of the newly emerging low-dimensional and molecular materials, the mass production of crystals with a desirable shape is still challenging. Here, a universal and high-yield method to grow functional single crystals with controlled dimensions is provided that can be directly integrated into a device. By utilizing a polymeric flux in combination with a compressed growth space, numerous materials can be grown into size-controllable single crystalline flakes, with millions produced in one batch. This scalable growth method shows promise for the large-scale integration of micro-single-crystals as functional components, as exemplified by the construction of a 5 in. field-effect transistor array.

Single-crystalline nanoflakes assembled CuS microspheres with improved sodium ion storage

Crystalline is of utmost importance for the electrochemical properties of anode materials. However, the effect of single or poly crystalline structure on the sodium ion storage of CuS is not yet deeply investigated. In this work, CuS microspheres assembled by single/poly crystalline nanoflakes are successfully synthesized by hydrothermal method. Their corresponding sodium ion storage abilities are systemically tested. The results reveal that CuS microspheres assembled by single-crystalline flakes exhibit superior electrochemical performance due to its highly order crystal lattice and complete structure integrity. Compared with poly-crystalline structure, the single-crystalline flakes show an enhanced diffusion rate of sodium ion, which leads to an excellent rate performance. Meanwhile, structural integrity of single-crystalline flakes results in a high mechanical strength, which brings long cycling stability for CuS microspheres. Consequently, single crystalline flakes assembled CuS microspheres could deliver a high capacity of 465 mAh g−1 under 0.1 A g−1, and 248 mAh g−1 under 5.0 A g−1. A highly reversible capacity of 364 mAh g−1 could be reached over 300 cycles under 1.0 A g−1. This work provides evidence that the sodium ion storage capability of assembled CuS microspheres could be improved by tailoring the crystalline degree of the building unit.

Synthesis and photochemical modification of monolayer thin MOF flakes for incorporation in defect free polymer composites.

Metal-organic frameworks (MOFs) with benzophenone linker molecules are characterized by their ability to undergo photochemical postsynthetic modification. While this approach opens up almost unlimited possibilities for tailoring materials to specific applications, the processability of the large particles is still lacking. In this work, we present a new approach to fabricate micro flakes of the stable Zr-bzpdc-MOF (bzpdc = benzophenone-4-4'-dicarboxylate) with a thickness of only a few monolayers. The crystalline and nanoporous flakes form dispersions in acetone that are stable for months. Embedding the flakes in polymer composites was investigated as one of many possible applications. Zr-bzpdc-MOF micro flakes were decorated with poly(dimethylsiloxane) (PDMS) via a photochemical postsynthetic modification and incorporated into silicon elastomers. The PDMS functionalization allows covalent cross-linking between the MOF and the polymer while maintaining the porosity of the MOF. The resulting hybrid materials provide defect-free interfaces and show preferential adsorption of CO2 over CH4, making them attractive for gas separation or sensing applications. The work should serve as a basis for bringing bzpdc-MOFs into real-world applications - in polymeric membranes, but also beyond.

Succeeded high-temperature acid hydrolysis of granular maize starch by introducing heat-moisture pre-treatment

Acid hydrolysis is a crucial method for modifying granular starch, but it is often conducted at low temperatures (below 55 °C) for an extended period of time to prevent crystallinity loss. The high-temperature acid hydrolysis (HTAH) behavior of heat-moisture treated (HMT) starch at 69 °C was investigated for the first time. The crystalline structure of starch was enhanced by HMT, confirmed by its rheological, thermal, and infrared Fourier transform spectroscopy results. The amorphous structure of HMT starch was preferentially hydrolyzed with high reactivity, related to a fast hydrolysis stage (4.17 × 10−2 min−1). And the crystalline flakes were separated from starch granules, accompanied by strengthened molecular interactions. HMT starch was transformed from 16.98 μm granules to 158 nm thick and 2.57 μm broad flakes with a 6.40 % increase in crystallinity after 40 min of hydrolysis. For native starch, the HTAH destroyed the crystalline structure due to gelatinization, resulting mainly gelatinous aggregates. These evidenced that the hydrolysis of granular starch was successfully performed at a relatively high temperature by introducing heat-moisture pre-treatment. This study could provide a novel perspective on the combination of increasing temperature and pre-treatment for granular starch hydrolysis intensification design, as well as a strategy for efficiently preparing small-sized crystalline starch, which has promising applications in Pickering emulsion and material filler.